Monoazo dyes for synthetic fibers



United States Patent 3,346,552 MONOAZO DYES FOR SYNTHETIC FIBERS James M. Straley, David J. Wallace, and Max A. Weaver,

Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Aug. 17, 1964, Ser. No. 390,211 Claims. (Cl. 260158) ABSTRACT OF THE DISCLOSURE Benzothiazolylazophenyl compounds are useful as dyes for hydrophobic textile materials and are characterized by a heterocyclic group attached to the coupler moiety and having the formula --NCZ wherein Z represents the carbon atoms completing a pyrrolidinono radical, a piperidono radical, or a phthalimidino radical.

This invention relates to azo compounds particularly useful as dyes for textile fibers.

The azo compounds have the following general formula wherein R represents a 2-benzothiazolyl radical unsubstituted or substituted, ie.,

Ar \O- in which Ar is an ortho-arylene radical of the benzene series, including ortho-phenylene and ortho-phenylene substituted by radicals such as alklsulfonyl, e.g., lower alkylsulfonyl, nitro, aliphatic acylamido, e.g., acetamido, cyano, thiocyano, sulfonamido, sulfonyl, lower cyanoalkylsulfonyl, halogen, lower alkylsulfonamido, lower alkoxy, lower alkyl, lower hydroxyalkyl, lower alkylthio, lower trifluoroalkyl, lower cyanoalkyl, lower carbalkoxy.

R represents a phenylene radical including, for example, 0-, mand p-p-henylene radicals and o-, mand p-phenylene radicals substituted with groups such as alkyl and substituted alkyl particularly lower alkyl of 1 to 4 carbon atoms, e.g. m-tolylene m-tolyleneO- alkoxy and substtuted alkoxy particularly lower alkoxy of 1 to 4 carbon atoms, acylamido such as acetamido, halogen including chlorine and bromine.

R represents hydrogen or an alkyl radical especially lower alkyl of 1 to 4 carbon atoms, and substituted alkyl such as lower hydroxyalkyl, lower alkoxyalkyl, lower acyloxyalkyl, lower alkylsulfonyl, lower carboxamidoalkyl, lower cyanoalkyl, lower chloroalkyl and bromoalkyl, lower acetoxyalkyl, lower carbalkoxyalkyl, R represents lower alkylene of 1 to 4 carbon atoms. Z represents a chain of carbon atom which together with hip 0 are necessary to complete a pyrrolidinono radical, a piperidono radical, or a phthalimidino radical, such as propylene, iso-propylene, butylene,

3,346,552 Patented Oct. 10, 1967 wherein R R R and Z have the meaning given above.

The above coupling components in which the ring is monocyclic, can .be prepared by reacting aniline or an aniline derivative with butyrolactones or caprolactones as described in our co-filed US. patent application Ser. No. 390,212. For example, butyrolactone can be refluxed with an N-[i-arninoethylaniline compound with removal of water to obtain the corresponding N-B-pyrrolidinonoethylaniline compound. The above coupling components in which the ring -NCZ is bi-cyclic can be prepared by reacting an N-aminoalkylaniline with phthalide or substituted phthalides such as chlorophthalide or an alkoxyphthalide, as described in our above co-filed application. For example, an N-B-ethylaniline compound and phthalide can be heated in the presence of sulfanilic acid while water is removed to yield the corresponding N-fl-phthalirnidinoethylani1ine compound.

The azo compounds can be expected to possess properties distinct from similar azo compounds in which the ring is connected directly to the benzene nucleus of a coupler in that they have better affinity and light fastness for polyesters.

2-aminobenzothiazole, 2-amino-6-methylsultonylbenzothiazole, 2-arnino-6-ethylsulfonybbenzothiazole, 2-amino-6-n-propylsulfonylbenzothiazole, 2-amino-6-n-butylsulfonylbenzothiazole, 2-aminobenzothiazole-6-N-methylsulfonamide, 2-aminobenzothiazole-6-N-ethylsulfonamide, 2-aminobenzothiazole-6-N-n-propylsulfonamide, 2-aminobenzothiazole-6-N-n-butylsulfonamide, 2-amino-5-methoxybenzothiazole, 2-amino-6-methoxybenzothiazole, 2-amino-6-ethoxybenzothiazole, 2-amino-6-n-propoxybenzothiazole, 2-amino-6-n-butoxybenzothiazole, 2-amino-4-rnethylbenzothiazole, 2-amino-6-methylbenzothiazole, 2-arnino-6-ethylbenzothiazole, 2-amino-6-n-propylbenzothiazole, 2-amino-6-n-butylbenzothiazole, 2-amino-6-fi-hydroxyethylbenzothiazole, Z-amino-6-'y-hydroxypropylbenzothiazole,

Z-amino-6--hydroxybutylbenzothiazole, Z-amino-6-acetylaminobenzothiazole, 2amino6-n-propionylaminobenzothiazole, 2-amino-6n-butyrylaminobenzothiazole, 2-amino-6-thiomethylbenzothiazole, Z-amino-6thiocyanobenzothiazole, 2-amino-o-cyanobenzothiazole, 2-amino-6-trifiuoromethylb enzothiazole, 2-amino-6-chlorobenzothiazole, 2-amino-4,6-dichlorobenzothiazole, 2-amino6-nitrobenzothiazole, 2-amino-4,7dimet-hoxybenzothiazole, 2-amino-5,6dimethoxybenzothiazole, 2-amin0-4,7-diethoxybenzothiazole, 2-amino-G-fi-cyanoethylthiobenzothiazole, 2-amin0-6-fi-cyanon-propylthiobenzothiazole, 2-amino-6-'y-cyanopropylthiobenzothiazole, 2-amino-6-p-cyanoethylsulfonylbenzothiazole, 2-amino-6v-cyanopropylsulfonylbenzothiazole, 2-amino-6 ({3, -dihydroxypropylthio)benzothiazole, 2-amino-6 (5, -dihydroxypropylsulfonyl) benzothiazole, 2-amino-6-,8carboxyethylthiobenzothiazole, 2-amino-6-fi-carb amylethylthio benzothiazole, 2-amino-6-B-dimethylcarbamylisopropylthiobenzothiazole and 2-amino-4,6-dimet-hylbenzothiazole are representative of the Z-aminobenzothiazole compounds used in the preparation of the azo compounds of our invention.

The azo compounds can be used for dyeing textile mate rials including synthetic polymer fibers, yarns and fabrics giving fast shades when applied by convention dyeing methods to cellulose ester, polyamide and polyester fibers. When the azo compounds are used for dyeing such hydrophobic materials, they should be free of watersolubilizing groups such as sulfo and carboxyl groups. In general, the dyes have good fastness, for example, to light, washing, gas (atmospheric fumes) and sublimation.

The following examples will serve to illustrate the preparation of representative intermediates and azo compounds of our invention.

Example 1 6.84 g. 2-amino-6-methylsulfonylbenzothiazole was suspended in 72 ml. water and 42.8 ml. conc. H SO was added, with stirring. The amine dissolved. The solution was cooled to C. and a solution of 2.52 g. NaNO N fi r CN=N N A3-CH2 CHSSOI \C2H4N/ S CH3 CH CH Example 2 0.76 g. sodium nitrite was added portionwise to 5 ml. conc. H 80 This solution was cooled in an ice bath and 10 ml. 1:5 acid was added, keeping the temperature below 20 C. This solution was cooled to 5 C. and 1.75 g. 2- amino-6cyanobenzothiazole was added, followed by 10 ml. 1:5 acid 1 part propionic:5 acetic). The mixture was stirred 2.5 hr. at ice-bath temperature. It was then added, with stirring to a chilled solution of 2.71 g. -1-[B (N-ficyanoethyl N-m-toluidino)aminoethyl]2-pyrrolidinone in 25 ml. 1:5 acid. The coupling was neutralized with solid ammonium acetate and allowed to react at ice-bath temperature for 2 hr., at room temperature for .5 hr. It was then drowned with water, filtered, washed with water, and dried. The product dyes cellulose acetate and polyester fibers deep red shades of excellent fastness. The product has the formula C 1 C Example Substituent on R Oup er omponent Color R1 Ra a Z Phenylcne CHzCI'IzCN CI 2CH2- CH CH CH R d. m-Tolylene omomcrv ornonr onionioni Rid. m-CH O-phenylene CHzCHzCN CHZCIIP CI-IzCHzCI-Ir Violet m-Cl-phenylene CIIQOHzCN CHgCHr CHZCHZCHP Red. 2-CH OSCH3-phenylene C H CHZCH CIIZCHZOHP Violet m-NHCOCH pl1enylene C H CHzCHr- CH CHzCIIr Do. O-TOlylGIlQ H OH CH C}I2CH2CHZ Red. 2,5d1-0CH phenyle CzHs OHZCHP CHzOH CI-Iz- Violet CHzCHzOH CHzCHr CHgCHzCHr Red. CHgCHgCl CHsOHr CHzCHaCHz- Red. CHgCHzOCHs CHgCHr- CHgCHgCH-r- Red. CHzCHzOOzCzH5 CHzCHr CHzCHzCHr Red. CHzCHzCHzBI CHzCHr- CHgCHzCHr Red. CHzCHzSOgCHz CHzCHz- CHgCHzCHz- Red. H CHzCH CHZCHZCHF Red. CH CH CONH CHzCHr CH CH CH Red. 2H5 CHzCHzCHz- CHzCHzCHr Violet ([3113 20 6-NO2 CzHa CHzCHOHr- OHzCHzCHr- Do.

3 21 fi-SOzNHa CzHa CHzCHz- CHCHzCHz- Pink.

22 6-SO2NH2 CzHa CHzCHr- CHzOHzCHzCHr D0.

23 fi-SOzNHz C2H5 OHzCHz- D0.

CHz-

. Coupler Component Example Substituent on 'R Color 1 Ra R; Z

24 6SO2NH2 m-Tqlylene -C H OH CH Ol Pink.

25 esomn. do -o.rr.' CH2CHz CH3 Do.

26 G-SOzCHzCHzOH (l0 CzH5 -CHzCHz- OCH3 D0.

-CHz- 6-SOzCH2CH2OH CHzCHz -CH CH CH2- D0. 6-SO2C4H9 CHzCHz- CH2CHzCH2- D0. 6'SO2C H9 -CH2CHz CHzCHzCHg- D0. G-SOzCHzOHzCN --CH2CHz- -CH2CH2CH2 D0. 6-SO;:N(OH3)2 CH2CH2 -CH2CH2GH2 D0. 6-CH CHzCHz -CHCHzOHz- Red. None CHzCI-Iz CH2CHzCHz- Red. 6-OCH3 CH2CH2 CH2CH2CH2 Red. 6-OCH3 ""CHZCHF -OH2OH2CH3 Red. 6-SO2CH2CH2GN -CH2CHz- -'CH2CHzCH2 Pink. 4,6-dichloro CH2CHZ CH2CHZCH2 Red. 6-bromo -CHzCHz CHzCH2CHz- Red. 4,6-dimethyl CHgOH CI'I2CH2OH2 Red. fi-SCHzCHzCN OHzCHz OHzCHzCHz Red. fi-NHOOCH; CH2CHz- -CH2CH2CH-z Red. A-CHa-fi-NO: --CHzCHz CH2CH2CHz Violet 43 6NO2 CHzCHz- D0.

44 G-SdzCHa l -CHaCHOHCNgC1 CH CH2 CH2CHzCH2- Red. 45 6-SOzCH Phenyleue -CH2CHOHCNzCl CH2CHz -OHzCHzCHz- Red.

It will be apparent from the above description of the invention that in the azo compounds having the general formula above, the substituents attached to R, R R R and Z are not critical and serve primarily as auxochrome groups to control the color of the azo compounds, and compounds which contain the disclosed substituents are especially useful as textile dyes. The fundamental properties of the azo compounds are attributed to the whole molecule of the azo compound to which the radical is indirectly attached.

dispersions in the manner of the so-called dispersed dyes. However, coloration can also be effected, for example, by incorporating the azocompounds into the spinning dope and spinning the fiber as usual. The azo compounds of our invention have varying utility as dyes. The degree of utility varies, for example, depending upon the material being dyed and the formula of the azo compound. Thus, for example, all the dyes will not have the same degree of utility for the same material.

Cellulose esters which can be dyed with the azo compounds include cellulose aliphatic carboxylic acid esters having 2 to 4 carbon atoms in the acyl groups thereof, by

The azo compounds of the invention may be used for dyeing hydrophobic fibers such as linear. polyester, cellulose ester, acrylic, polyamide, etc., fibers in the manner described in US. Patents 2,880,050, 2,757,064, 2,782,187 and 3,043,827. The following example illustrates methods by which the azo compounds of the invention can be used to dye textile materials.

0.1 gram of the dye is dissolved in the dye pot by warming in 5 cc. of ethylene glycol monomethyl ether. A 2% sodium-N-methyl-N-oleyl taurate and 0.5% sodium lignin sulfouate aqueous solution is added, with stirring,

until a fine emulsion is obtained. Water is then slowly' added to a total volume of 200 cc. 3 cc. of Dacronyx (a chlorinated benzene emulsion) are added and 10 grams of a textile fabric made of Kodel polyester fibers are entered. The fabric is worked 10 minutes without heat and then for 10 minutes at 80 C. The dyebath is then brought to the boil and held at the boil for one hour. Following this, the fabric is rinsed in warm water, then scoured in an aqueous 0.2% soap, 0.2% soda-ash solution. After scouring, the fabric is rinsed with water and dried. Accordingly, since the azo compounds of the invention are water-insoluble, they can be applied from aqueous which we mean to include, for example, both partially hydrolyzed and unhydr olyzed cellulose acetate, cellulose propionate and cellulose acetate-butyrate.

Polymeric linear polyester materials of the terephthalate type are illustrative of thelinear aromatic polyester textile materials that can be dyed with the new azo compounds of our invention. The terephthalate fibers sold under the trademarks Kodel, Dacron and Terylene, for example, in the form of filaments, yarn and fabric, for example, are illustrative of the polyester textile materials that can be dyed. Kodel polyester fibers are more particularly described in US. Patent 2,901,446. Dacron and Terylene polyester fibers are described, for example, in US. Patent 2,465,319. The polymeric linear polyester materials disclosed in US. Patents 2,945,010, 2,957,745 and 2,989,363, for example, can be dyed. The linear aromatic polyester materials specifically named have a melting point of at least 200 C. Nylon, in fiber yarn and fabric form, is representative of polyamides which can be dyed with the azo compounds.

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spiirt and scope of the invention as described hereinabove, and as defined in the appended claims.

What we claim is: 7

1. A20 compounds having the formula wherein R=a 2-benzothiazolyl radical,

R =a phenylene radical,

R =a member of the class consisting of hydrogen and a lower alkyl radical,

R =lower alkylene, and

Z=the carbon atoms which with complete a pyrrolidinono radical, a piperidono radical, or a phthalimidino radical, said compounds being free of water-solubilizing groups.

2. A20 compounds having the formula of claim 1 wherein R represents a lower alkyl radical and Z represents the carbon atoms which with wherein R=a Z-benzothiazolyl radical,

R =a p-phenylene radical,

R =lower alkyl,

R =lower alkylene, and

Z=the carbon atoms which with complete a pyrrolidinone radical, said compounds being free of water-solubilizing groups.

4. The azo compound having the formula CHaSOz CHzCH:

5. The azo compound having the formula CHzOH,

6. The azo compound having the formula N /CzH4N ON=N-ON omens NOC2H4SO2 I \CZHE S CH3 7. The azo compound having the formula 0 H o N C-N= N\ CH OZN (B 02m 2 8. The azo compound having the formula C N=N@ N am 01130 onriN I S OH:

CHBCH? 9. The azo compound having the formula i CzHgN CH3 CHzCHz 10. The azo compound having the formula /C2H4CN O CN=N -N\ CCHI OHSSOZ \s CZILN I cHiCHi References Cited UNITED STATES PATENTS 3,161,631 12/1964 Straley et al 260-158 CHARLES B. PARKER, Primary Examiner.

D. PAPUGA, Assistant Examiner. 

1. AZO COMPOUNDS HAVING THE FORMULA 